Process for treating a &#34;nitrile alloy&#34; article with a polyphenolic antistatic agent and product obtained thereby



July 31, 1962 s. A. MURDOCK ET AL 3,047,426

PROCESS FOR TREATING A "NITRILE ALLOY" ARTICLE WITH A POLYPHENOLICANTISTATIC AGENT AND PRODUCT OBTAINED THEREBY Filed July 29, 1958 IN VEN TORS 5/00 /eg ,9. Murdock H TTORNEYS This invention lies primarily inthe synthetic textile fiber field and contributes particularly to theart of beneficially treating certain varieties of such manufactures, aswell as related shaped articles, to render them nonsusceptive, or atleast substantially less propense, to accumulate charges of staticelectricity when they are in a dry state or condition. Moreparticularly, the present invention has reference to the destaticizationof certain of the nitrile alloy types of acrylonitrile polymer fibersand the like and related shaped articles and structures.

Amongst the achievements that crown the progress of the man-madeartificial silk and synthetic fiber industry has been the developmentand attainment of certain of the so-called nitrile alloy varieties ofsynthetic textile fibers. Such synthetic fibers, as is known andpursuant to the indicated generic description therefor, are basedlargely and essentially on fiber-forming acrylonitrile polymers,especially those that contain in the polymer molecule at least about 80percent by weight of acrylonitrile, advantageously polyacrylonitrile,that have been beneficially alloyed or blended with various ameliorativeadditaments, adjuvants or components that, generally, are polymeric innature and which are intimately and permanently associated or coupledwith the acrylonitrile polymer substrate by either physical or chemicalmeans, or both. Predominantly desirable and advantageous members of thenitrile alloy class of synthetic fibers and the like are those,hereinafter more fully delineated, that are comprised of acrylonitrilepolymer substrates and which contain minor integrant proportions ofeither, or both, various N-vinyl lactam polymers and copolymers orderivatives thereof or various N-vinyl-Z-oxazolidinone polymers andcopolymers or derivatives thereof.

Such nitrile alloys, without compromise of the outstanding physical andother properties and characteristics as textile fiber materials and thelike that are inherently obtainable in and with acrylonitrile polymers,are most advantageously bestowed with many desirable and peculiaradditional features and qualities that are quite foreign to conventionalacrylonitrile polymer (or acrylic) fibers. Most noteworthy andremarkable of their repletion, especially in view of their acrylonitrilepolymer derivation and extraction, is the most proficuous and felicificcapability of the referred-to nitrile alloy fibers to be highlyreceptive of and excellently dyeable with any of a wide variety ofdyestuffs. For example, by conventional procedures and without resort tospecialized methods or extraordinary techniques, the described nitrilealloy fibers may be easily and satisfactorily dyed with most acid, vat,acetate, direct, naphthol, sulfur and premetalized dyestuffs.

In common with other synthetic, essentially hydrophobic, polymerictextile fibers and the like articles, however, the above-mentioned typesof nitrile alloy fibers, when in the dry state, tend to accumulatecharges of static electricity upon being handled. This, of course, andas can be readily appreciated, engenders various difficulties of thewidely recognized variety in their handling and use, both in theirprocessing in and through various textile and the like operations and inconnection with their application as finished textile articles(including filaments, fibers, yarns, threads, cords and the ts tat ice3,fi47,42fi ?atented July El, 1962 like and cloth and fabric constructedtherefrom) as Well as in other varieties of shaped articles andstructures. Such characteristics tend to lessen the otherwise generalattractiveness of the nitrile alloy fibers and other articles. Forexample, besides the difficulty in handling during various manufacturingoperations and use applications, many individuals may object to thedelitescent electrical shocks that they may be subject to or the sparksthat may be discharged when they serve as the effective grounding meansfor articles comprised of nitrile alloys when there is a considerableaccumulation of electrical charges on the articles. Furthermore,electrostatically charged articles of any synthetic polymer, includingthe nitrile alloys, display great tendencies to collect dust and dirtand to have undesirably high degrees of soil retentivity. As isapparent, such behavior limits their adaptability for being utilized ina completely satisfactory manner for many apparel, upholstery, homefurnishing, decorative, and other uses.

It would be advantageous, therefore, to provide an effective andeificient means for destaticizing synthetic textile fibers and the likeand related articles comprised of the indicated varieties of nitrilealloys.

Pursuant to the accomplishment of this and related desiderations, it isthe primary object of the present invention to advance the art andtechnology of synthetic textile fibers by providing an improved methodfor destaticizing and benefitting the indicated varieties of nitrilealloy fibers and the like and related shaped articles as well as thedestaticized products resulting from practice of the method.

To this end, nitrile alloy fibers and other shaped articles that arecomprised of acrylonitrile polymer substrates, and especially thosewhich contain minor proportions of either, or both, N-vinyl lactampolymers and copolymers or derivatives thereof orN-vinyl-2-oxazolidinone polymers and copolymers or derivatives thereof,may advantageously and most effectively be destaticized by finishingthem with certain varieties of polyphenolic polymers or condensationproducts which contain in their structure either polyethylene glycol orsulfonate groups or both and in which there are available a plurality offree phenolic hydroxyl substituents, as hereinafter more fullydescribed. The antistatic agents that are employed in the practice ofthe present invention have the ability to complex with the nitrile alloybase or substrate, such as a filamentary article, over which they areapplied by both physical and chemical means so as to become attached tothe substrate in a very durable and difficult-to-remove manner. As aconsequence of their remarkable substantivity, the antistatic agentsused in the practice of the present invention secure an efiicient andliterally permanent destaticizing effect on the nitrile alloy articleswith which they are combined. in addition to destaticizing the fiber,the antistatic agents used in the practice of the invention tend toincrease the washfastness of the treated article when the applicationhas been made subsequent to dyeing. Conversely, regardless of when theapplication is made with respect to coloration of the nitrile alloyarticle, the antistatic agents improve its resistance to becomingstained with many dyestuffs and coloring agents. This may be highlyadvantageous when it is desired for the nitrile alloy article to remainin a naturally uncolored or white condition. Application of theantistatic agents of the present invention exerts no deleteriousinfluence or other interfering effect upon the general utility andproperties of the treated fiber. A destaticized nitrile alloyfilamentous article in accordance with the present invention isillustrated in the sole FIG- URE of the hereto attached drawing.

Without being limited to or by the specific embodiments and modes ofoperation set forth, the invention is illustrated in and by thefollowing didactic examples, wherein, unless otherwise indicated, allparts and percentages are to be taken on a weight basis.

EXAMPLE A A phenol-formaldehyde-novolak type of condensation product ofthe soluble, low molecular weight variety was prepared and subsequentlyesterified with about 1.8 moles of ethylene oxide added per unit ofphenol in the condensation product. The novolak product that wasesterified was obtained by refluxing about 898 grams of the common,trifunctional phenol with about 464 grams of a 37 percent aqueoussolution of formaldehyde (to provide about 0.6 moles of HCHO per mole ofC H OH) in the presence of about 4.5 grams (10.3 ml. of 12 N)hydrochloric acid. The preparation was accomplished in the conventionalmanner. After phase separation, the resulting resinous condensationproduct was removed, washed free of chloride with water, anddevolatilized by heating it to a temperature of about 130 C. under anabsolute pressure of about 2 millimeters of mercury. About 729 grams ofnovolak product was thereby obtained, having a molecular weight of about322 (as determined by cryoscopic methods) in which the mole ratio ofphenol to formaldehyde was about 1:05, respectively. The productcontained an average of about 4 phenolic units per molecule.

About 580 grams of the resulting novolak product was dissolved in 290grams of dioxane. In this solution there was incorporated about 1.74grams of sodium hydroxide (obtained by addition of about 3.5 grams of a50 percent aqueous solution of NaOH). The ingredients were charged intoan Aminco rocking-type reactor wherein they were heated until atemperature of about 130 C. was attained. At this point, ethylene oxidewas admitted under pressure until a total of about 608 grams (13.8moles) was charged over a 20 minute period. This quantity of ethyleneoxide constituted about 2.5 moles of alkylene oxide per phenolic OH inthe novolak resin, Upon addition of the ethylene oxide, a rapidexothermic reaction ensued. This elevated the temperature of thereaction mass to about 200 C. Within about 30 minutes after the additionof the alkylene oxide, the reaction mass returned to a temperature ofabout 130 C., whereat it was synthermally maintained for an additionaltwo hour period. The etherified novolak product was then recovered fromthe reaction mass and, upon devolatilization, was found to have a weightof about 1018 grams. This corresponded to a weight gain on the modifiednovolak resin of about 438 grams and indicated that an average of about1.8 moles of ethylene oxide had actually been added on per phenolic OHof the starting novolak. The resulting composition, upon the basis ofreasonable information and belief, was presumed to have a generalstructure corresponding to the following formula:

(C2H4O)7..2 Ion CH2 l\ CH2 on About 20 grams of the etherified novolakwas dissolved in about 80 grams of acetone to form a cloudy solution.Upon the addition of 100 grams of water, a clear, light yellow solutionwas obtained. The resulting solution contained about percent of thedissolved, solid, novolakethylene oxide reaction product or adduct.About 100 grams of the resulting 10 percent etherified novolak solutionwas diluted with an additional 100 grams of a mixture of about equalproportions by volume of acetone and water in order to form anapplicating solution of the antistatic agent for a nitrile alloy fiber.

A sample of about 17 grams of a poly-N-vinyl-2-pyrrolidone-impregnatedpolyacrylonitrile nitrile alloy fiber 4% was immersed in the applicatingsolution of the etherified novolak antistatic agent for about 30 secondsat room temperature. After this, it was removed and the excess solutionsqueezed out. About 9 percent of the antistatic agent, based on theweight of the fiber, was thus picked-up on the fiber structure. Thetreated fiber was then dried at about C. to form the destaticizedarticle.

The nitrile alloy fiber sample that was treated had been prepared byimpregnating filamentary structures that were in aquagel condition afterhaving been salt-spun and wet-stretched in and with an aqueous solutionof poly-N- vinyl-2-pyrrolidone that contained about 3 percent of thedissolved vinyl lactam polymer. The polyacrylonitrile aquagel fiber thatwas so-employed had been obtained by extruding a spinning solution offiber-forming polyacrylonitrile comprised of about 10 parts of thepolymer dissolved in 90 parts of a 60 percent aqueous solution of Zincchloride through a spinnerette having 750 individual 6 mil diameterorifices into an aqueous coagulating bath that contained about 42percent of dissolved zinc chloride to form a multiple filament tow.After being spun, the tow bundle of coagulated polyacrylonitrile aquagelfiber was washed substantially free from salt from the coagulating bath.It was then wet-stretched for orientation to a total stretched lengththat was about 12 times its original extruded length. The aquagel fiberwas then passed through the mentioned aqueous impregnating bath of thedissolved polyvinylpyrrolidone adjuvant so as to become impregnated withabout 8 percent, based on the dry weight of the resulting nitrile alloyfiber, of the poly-N-vinyl-Z-pyrrolidone. Following the impregnation,the aquagel fiber was irreversibly dried at C. to destroy the Waterhydrated structure and convert it to a finished fiber form. The finallyobtained, three denier, nitrile alloy fiber product had a tenacity ofabout 4 grams per denier, an elongation of about 30 percent and a wetyield strength of about 0.8 gram per denier. After application of theetherified novolak antistatic agent in the above-indicated manner, thephysical properties of the fiber remained substantially unchanged.Likewise, other of its characteristics, including its hand (or feel tothe touch) and general visual appearance were unaltered.

Following application of the antistatic agent, a portion of the treatedfiber sample was scoured for about one hour at the boil using 0.5percent detergent on the weight of the goods contained in a bath havinga 30:1 water volume to fiber weight ratio, respectively. The detergentthat was employed was 'Igepal CA-630 (an alkylphenoxypolyoxy alkyleneglycol, non-ionic detergent obtained from General Aniline and FilmCorporation).

The antistatic properties of the destaticized and scoured nitrile alloyfiber were then determined by measuring the electrical conductance ofthe fiber product at various humidities. As will be appreciated by thoseskilled in the art, the basis for such a test is that all fibers have atendency to generate static electricity upon being handled in the drystate. Only those that are possessed of sufficient electricalconductance to dissipate the charge as quickly as it forms are nothampered by the bothersome effects of static electricity. Thus, ameasure of the electrical conductance of a fiber is a good indication ofits ability to dissipate static electricity. The conductivity of thefiber sample that was tested, along with the conductivities of variousother samples determined for purposes of comparison, was found bymeasuring its electrical resistance. Resistance, of course, is thereciprocal quantity of conductivity. In order to permit various fibersamples to be compared on a common basis, the conductivities of thesamples tested were actually measured as volume resistivities accordingto the following formula:

Volume resistivity (Resistance) (Cross-sectional area) U YAA on a dryweight basis).

The units of volume resistivity are ohm-c1n. /cm. The actual resistivityof each sample was determined after the sample being tested wasconditioned for 72 hours at the particular temperature and relativehumidity conditions involved by tautly connecting a web-like sample ofthe yarn between two electrodes, each of which were 9 cms. long, spacedparallel 13.5 ems. apart, and across which three was applied a 900 voltdirect current potential. For purposes of comparison, the volumeresistivities of cotton, wool, the undestaticized nitrile alloy fiber,and an ordinary unmodified polyacrylonitrile fiber (obtained in the samegeneral way as the nitrile alloy fiber but without having thepoly-N-vinyl-Z-pyrrolidone incorporated therein) were also tested in theindicated manner with the destaticized fiber sample that had beenprepared in accordance with the present invention. The results are setforth in the following tabulation which indicates the volume resistivityobtained at various relative humidities (RH) at 24 C. of each of thesamples tested.

TABLE I Volume Resistivity of Various Fiber Samples Compared to NitrileAlloy Fibers Destaticized With Ethylene Oxide Etherified NovolakAntistatic Agent As is apparent from the foregoing, the destaticizedfiber sample, even after being severely scoured, had electricalconductance properties much superior to the nitrile alloy fiber that hadnot been treated or to ordinary unmodified polyacrylonitrile and even towool. Its static properties were only slightly poorer than cotton. Thus,a very practical and significant increase in electrical conductivity andresulting decrease in propensity to accumulate static electricity Wasobtained in the treated nitrile alloy fiber.

When the destaticizing agent was attempted to be ap plied to theordinary polyacrylonitrile fiber, it was found to have very pooradherence thereon and very little substantivity thereto. This, ofcourse, precluded the realization of satisfactory results in suchoperation.

EXAMPLE B Following the procedure of Example A, about 8 percent of thesame antistatic agent was padded onto the same nitrile alloy fiber froma 5 percent applicating solution of the antisatic agent that had beenprepared using the half-acetone, half-water diluent for the initiallyobtained percent solution of the etherified novolak adduct that wasdescribed in the first example. After the padding, the fiber sample wasdried at 60 C. for about an hour. It was then constructed into a knitcloth which was divided into 3 separate portions (of about 5 grams eachEach of the portions were subjected to various washing and scouringtreatments, after which the electrical conductances of each of thesamples was measured in the above-indicated manner and compared to wool,cotton and an undestaticized nitrile alloy fiber sample. The firstportion of the destaticized sample was scoured for minutes at 60 C. anda 1 percent aqueous solution of Tergitol NPX (an alkylphenylpolyethyleneglycol ether, non-ionic detergent obtained from Union Carbide ChemicalCompany). The second sample was subjected to a single wash test whichconsisted of placing the sample into a one quart stainless steel vesselthat contained about 100 one-quarter inch steel balls and TABLE IIVolume Resistivity of Various Fiber Samples Compared to Several Washedand Seoul-ed Samples of Destaticized Nitrile Alloy" Fibers Volumeresistivity, ohm-cmfi/cm. Sample 47 percent 66 percent RH RH Securedportion of destatieized Nitrile Alloy yarn 8. 3X10 9 3. 6X10 9 Singlewash tested portion of dest-aticized Nitrile Alloy yarn 1.7)(10 W 5.7X10 9 Five times washed tested portion of destaticized Nitrile Alloyyarn 2. 9X10 8. 0X10 9 Undestaticized Nitrile Alloy yarn 2. 7X10 13 1.2X10 12 2. 7X10 5 5. 4X10 0 2X10 3.3)(10 EXAMPLE C Results similar .tothose in the foregoing examples may be obtained when the antistaticagent that is employed is of the following structure:

wherein n is a whole integer having an average value of at least 2,preferably between 2 and 8; and at least about A of the R substituentsare hydrogen with the requirement that at least three substituenthydroxyl groups are present in each molecule and the remainder of the Rsubstituents are polyethylene oxide groups containing an average ofabout 2 to 20, advantageously 2 to 10, ethylene oxide units peretherified substituent. As is apparent, and as will be appreciated bythose who are skilled in the art, the exact location of the phenylalkoxy groups relative to the alkylenic bridges are not necessarily inthe same positions on each of the rings, but may be either orthoorpara-relative to one another as may randomly occur in the preparation ofthe novolak. Likewise, as is indicated in the foregoing, at least threehydroxyl substituents must be contained in each molecule of the compoundso that at least a portion of the phenolic hydroxyl in the novolakremains free and unsubstituted with ethylene glycol groups. This ensuresthat the antistatic agent will have the desired complexing ability withand substantivity for the nitrile alloy article upon which it isapplied.

EXAMPLE D Results similar to those obtained in the first two examplesmay be realized when the antistatic agent, prepared and utilized in amanner analogous to that set forth in the foregoing, is comprised of theethylene oxide etherified reaction product of a polyphenolic polymersimilar to that set forth in Example C, with the exception that thebridging units are comprised of such difunctional radicals as thosederived from vinyl compounds, isopropenyl compounds, divinyl benzenecompounds or diisopropenyl compounds so that the resulting structureshave the following formula:

wherein R is selected from the group consisting of oxyethylene units andmixed oxyethylene-oxypropylene units; R is hydrogen or methyl with thelimitation that not more than one R is hydrogen in any one linkage; R"is selected from the group consisting of the same members as for R andhydrogen with the additional characterization that n is 2 and greater toabout 8 when R is hydrogen and n is 3 and greater to 8 when R is thesame as R; x is a number having an average value from 2 to 10 and y is anumber having an average value from to with the limitation that the sumtotal of x-i-y is from 2 to 2().

EXAMPLE E Results commensurate with those set forth in the first examplemay be obtained when the antistatic agent that is utilized is anethylene oxide ethen'fied polyphenolic polymer derived from suchbis-phenol type phenolic monomers as bis-phenol A(para,para-isopropylidene diphenol), bis-phenol sulfone(para,para-sulfonyl diphenol) or bis-phenol sulfoxide(para,para'-sulfinyl diphenol) that have been condensed with suchbridging agents as methylene, vinyl, isopropenyl radicals or by means ofdifunctional radicals from divinyl benzene or diisopropenyl benzene sothat the resulting product has a structure represented by the followinggeneric formula:

or propylene (CHCH -CH B is isopropylidene [C(CH sulfonyl (SO andsulfinyl (SO), 11 is 2 or more to 8 when R'=H; n is 3 or more to 8 whenR=R; R or R is H or C H and in which at least 30H groups are adjacentper molecule and at least one R is (C H O) per molecule when the valueof x is 2 to 10.

EXAMPLE F Excellent antistatic agents are obtained when the proceduresof Examples A and B are repeated excepting to employ as thedestaticizing substance that is applied to the nitrile alloy fiber, ahomopolymer of such difunctional monomers as vinyl or isopropenylphenols that has been reacted with ethylene oxide so that the antistaticetherified polyphenolic polymer product is of the formula:

on on OR" nca= (2-011 7 c-cn a R R wherein R and R are hydrogen oroxyethylene (C H O); R is hydrogen or methyl; and n is 2 or more toabout 8 and provided that at least three hydroxyl substituents arepresent in each molecule.

EXAMPLE G Results similar to those obtained in Examples A and B may berealized when the antistatic agent employed is a phosphorous-containingpolyphenolic polymer that is a condensation product of such phenolicmonomers as hydroquinone, bis-phenol A, bis-phenol sulfone, or bisphenolsulfoxide with difunctional bridging radicals derived from phosphorousoxyhalides, such as phosphorous oxychloride (POCI wherein the mole ratioof difunctional phenol to phosphorous is between about 3:1 and 1:1,respectively, preferably about 5:2, etherified with an average of 2 to20 moles of ethylene oxide per phenol unit in the condensed polymer sothat the resulting antistatic resinous product has a structural formulaaccording to the following:

R n (V) in which, when n is 2, R is hydrogen or para hydroxyphenyl and Ris a polyoxyethylene unit, i.e., ((1 1-1 0), in which x is a pluralinteger to 20, preferably from about 2 to 10,

and when n is 3 and greater to 8 at least 3 of the R units must behydroxyphenyl and the remaining R may be hydroxyphenyl, an alkali metal(lithium, sodium or potassium) or hydrogen; and R is polyoxyethylene.

XAMPLE H Poly(p-hydroxyphenol) substituted alkanes of the generalformula:

/i -o- R wherein n is an integer having a value from 2 to 6 and R, R andR" are hydrogen or para hydroxyphenyl groups with a total of from 3 to 6of the latter groups in the substituted alkane molecule, wherein atleast one or more in excess of 2 of the substituted para hydroxyphenylgroups have been etherified with an average of from 2 to 20 moles ofethylene oxide per phenol unit in the molecule causing part of thehydroxyls to be substituted with polyethylene oxide units in thefollowing manner:

wherein in has the indicated numerical value between 2 and 20,preferably up to about 10, so that the resulting ethylene oxide adducthas the general formula:

H uR

R (VI) wherein n is 2 or more to 8 and at least 2 of the R units must bepara hydroxyphenyl and at least one R must be polyoxyethylated oxyphenylin which in is a plural integer up to 20.

As is apparent from the foregoing, nitrile alloy articles treated inaccordance with the present invention, one of which is illustrated inthe accompanying drawing, retain the antistatic agent in a substantiallypermanent manner through the normal usage of the material. They haveexcellent antistatic properties and may be handled and employed readilywithout difiiculties due to accumulations of antistatic electricity.Furthermore, articles in accordance with the present invention retaintheir essential characteristics, including hand, and have no undesirableinfiuence on the other aesthetic characteristics of the fiber or otherarticle. As a matter of fact, as has been indicated, the treatment ofthe present invention improves the resistance to staining ordiscoloration of the treated article and generally benefits thewashfastness of an article that has been dyed when the application ofthe antistatic agent is made on the colored material. In thisconnection, it is generally beneficial to treat articles intended to bedyed with the antistatic agent after they have been dyed to a desiredshade of color in order to avoid dilficulties with dyeing proceduresthat may be involved if the destaticization is performed prior todyeing.

Any desired amount of the antistatic, etherified polyphenolic resins maybe employed on a nitrile alloy fiber or other shaped article. Usually itis beneficial to apply an amount between about 0.5 and 10 percent byweight of the antistatic agent, based on the dry weight of the shapedarticle being treated. In many cases, it may be more advantageous forthe amount that is used to be between about l.0 and 2.0 percent byweight.

Various techniques may be utilized for the application of the etherifiedantistatic agents of the invention which, if sufficiently oxyalkylated,are often water soluble. As has been illustrated, they may frequently beapplied from solution using a suitable solvent for the purpose such asvarious mixtures of acetone and water or water or acetone alone. Anypolar solvents may be used such as alcohol, lower ketones includingmethyl ethyl ketone and methyl isobutyl ketone, dioxane, cyclohexanol,etc. In an analogous manner, it is oftentimes possible for theapplication of the antistatic agent to be made from a dispersion usingwater or some other inert medium as a dispersant vehicle. Frequently, topercent of a dispersing agent on the weight of the dispersion may beeffectively employed. Thus, in the manner of conventional textile finishapplication, applicating formulations of the antistatic agent may beapplied directly to a running strand of a nitrile alloy fiber or othershaped article using a liquid jet or spray of the formulation. Ifdesired, applicating rollers and equivalent devices may be utilized forthe purpose. It may frequently be more convenient, however, particularlywhen dyed textile materials are being treated, to employ the applicatingformulation as a treating bath in which the nitrile alloy fiber article,including an article in the form of cloth or fabric, during any stage ofmanufacture or subsequent thereto, is immersed in order to pickup orbecome impregnated with the desired quantity of the antistatic agent.When cloth and fabric are being treated, it may be most convenient forthe application to be made in a manner analogous to conventional paddingtreatments.

The quantity of dissolved or dispersed solids that is present in theapplicating formulations of the antistatic agents may vary, dependingupon whether a solution or suspension is being employed. Ordinarily, itis suitable for the applicating solution or dispersion to containbetween about one-half and fifteen percent by weight, preferably betweenabout two and five percent of the antistatic agent, based on the weightof the solution or dispersion of applicating liquid. The application maybe made at normal room temperatures or at any other desired andpractical temperature. After its application on the nitrile alloy fiberor other shaped article, the antistatic agent is dried thereon toprovide the desired, destaticized product.

As has been indicated in the foregoing, the nitrile alloy fibers arecomprised essentially of the mentioned acrylonitrile polymer base whichhas been modified or alloyed with beneficial additaments or constituentswhich are adapted and calculated to provide the fiber product with itspeculiar and unusually advantageous properties. Various beneficialadditaments or constituents that are capable of securing the desirablecharacteristics of which the nitrile alloy fiber is possessed may be anyof several diverse types. For example, the beneficial constituent may bederived from and originate with a monomer or mixture of monomers,capable of being converted to a dye-receptive and possibly otherwisefunctional polymer product, which is graft or block copolymerized to andupon the already formed (and, with advantage, already fabricated)acrylonitrile polymer base. Alternatively, and with equal advantage, thebeneficial constituent may be a dye-receptive and possibly otherwisefunctional, polymeric product with which the essential acrylonitrilebase is graft or block copolymerized by graft copolymerization ofacrylonitrile or an acrylonitrile monomer mixture on or with the alreadyformed functional polymer in order to furnish the fiber-forming polymerproduct of which the nitrile alloy fiber is composed. Or, as a suitableand frequently quite satisfactory alternative, the already formedbeneficial additaments or constituents in the nitrile alloy fiber may bein the nature of polymeric adjuvants that are physically blended andintimately incorporated by any of several suitable procedures with theessential acrylonitrile polymer base. Such adjuvants may behomopolymeric, copolymeric or graft copolymeric substances which serveto augment at least the dyeability of the normally difiicult (if notimpossible) to dye acrylonitrile polymer base.

Amongst the most beneficial and advantageous of the nitrile alloy fibersare those that are comprised of the essential acrylonitrile polymerbase, particularly polyacrylonitrile, in which there has been intimatelyand permanently or substantially permanently incorporated minorproportions of up to about 20 or so percent by weight, based on theweight of the nitrile alloy composition, of any of the beneficialadditaments or constituents adapted to serve the desired purpose andprovide the beneficial result. Generally, such beneficial additamentsare employed primarily as dye-assisting adjuvants or components.Advantageously, they may be the polymerized products of such azoticmonomers, or mixtures thereof, as the several N-vinyl lactams includingsuch broadly related products as the N-vinyl-3-morpholinones; the N-vinyl-2-oxazolidinones; and certain of the N-vinyl-N-methyl-alkyl-sulfonarnides. Thus. the nitrile alloy may be comprised ofthe acrylonitrile polymer base that is prepared by graft or blockcopolymerization of acrylonitrile or an acrylonitrilecontaining monomermixture upon a minor proportion of an already formed polymer derivedfrom any of the indicated varieties of azotic monomers or theirmixtures. Or, as mentioned, it may consist of a graft copolymer productof any of the indicated varieties of azotic monomers on an alreadyformed and preferably already fabricated acrylonitrile polymer base.Advantageously, and frequently, with consummate suitability, the nitrilealloy fiber may be comprised of the acrylonitrile polymer base in whichthere is permanently incorporated by physical blending in minorproportion of any of the polymer products from the specified azotic 1 lmonomers or mixtures thereof, primarily as dye-assisting adjuvants.

Such species of nitrile alloy fibers are capable of being accuratelydescribed as synergetic and anisotropic clathrates that are composed ofa hydrophobic polymer in combination with a hydrophilic polymer. In suchvarities of the nitrile alloy fibers (as well as in other of the formsin which they may be obtained) there is a mutually enhancing cooperativeunion of a highly crystalline polymer which provides strength,durability, wrinkle recovery and high melting point in the fibers withan usually non-ionic polychelate that provides dye-receptivity as wellas moisture regaining powers for the fiber and other aestheticcharacteristics that lend to the wearing comfort of textile goodsmanufactured from the fiber. The nitrile alloy fibers have beendescribed by G. W. Stanton in an article entitled Zefran appearing inthe Textile Research Journal, volume XXVII, No. 9, for September 1957 atpgs. 703413. They have also been recognized as a distinct class ofman-made synthetic textile fibers in Textil Organon, September 1956, atpages 129130.

As indicated, the adjuvant or beneficial constituent in the nitrilealloy fiber may be homopolymeric in nature or it may be a straightcopolymer of any of the azotic monomers specified with other monoandpolyfunctional monomers. Adjuvants of this variety are ordinarilyphysically blended with the essential acrylonitrile polymer base inorder to secure the desired intimate incorporation of the beneficialconstituent and the resulting alloying effect in the fiber. Likewise,there may be similarly utilized for physical blending purposes adjuvantsor additaments that are graft copolymeric in nature and which consist ofvarious monomers that are graft copolymerized on substrates consistingof polymers of any of the indicated azotic monomers, such aspoly-N-vinyl-lactam substrates; poly-N-vinyl-Z-oxazolidinone substrates;and poly-N-vinyl-N-methylall ylsulfonamide substrates. Similarly, justas suitably, graft copolymeric additaments may be provided and employedwhen they consist of any of the specified or closely related azoticmonomers (such as Nvinyl lactam monomers, N-vinyl-Z-oxazolodinonemonomers and N-vinyl-N-methyl-alkyl-sulfonamide monomers) graftcopolymerized on other functional polymer substrates.

It is usually beneficial for the polymer products of the azoticfunctional monomers to be present as the beneficial component in nitrilealloy fibers in an amount that is in the neighborhood or range of fromabout to percent by weight, based on the weight of the nitrile alloycomposition. It is frequently quite desirable to employ a homopolymericN-vinyl lactam polymer, such as poly-N-vinylpyrrolidone (which may alsobe identified as poly-N-vinyl-Z-pyrrolidone or, with varied terminology,poly-N-vinyl-2-pyrrolidinone), poly-N-vinyl caprolactam, or somewhatrelated thereto, a poly-N-vinyl- 3-morpholinone; or a homopolymericN-vinyl-Z-oxazolidinone or poly-N-vinyl-S-methyl-2-oxazolidinone; or ahomopolymeric N-vinyl-N-methylalkylsulfonamide polymer such ashomopolymeric N-vinyl-N-methyl-methylsulfonamide; as the polymericadjuvant that is blended with the essential acrylonitrile polymer basein the nitrile alloy composition. When physically blended nitrile alloyproducts are prepared that utilize, as the beneficial additament orconstituent, copolymeric or graft copolymeric products of the indicatedazotic monomers, it is usually beneficial for the polymeric adjuvantsthat are employed to be those which are comprised of at least about 50percent or even as much as 80 or more percent by weight of the productsof the indicated constituents derived from the azotic monomers.

In addition to products of N-vinyl-pyrrolidone or N- vinyl caprolactam,other of the N-vinyl (or l-vinyl) lactams which may be utilized includesany of those (or their mixtures) that have been described or which areinvolved in U.S. Patents Nos. 2,265,450; 2,355,454 and fit 12 2,371,804.Particular mention may also be made of N- vinyl-S-methyl-pyrrolidone;N-vinyl-3,3-dimethyl gamma valerolactam; and N-vinyl piperidone.Particular mention may also be made of somewhat related products derivedin any of the ways described from N-vinyl-3-morpholinones of thestructure:

wherein each substituent R unit is independently selected from the groupconsisting of hydrogen, 1 to about 4 carbon alkyl radicals, 6 to about10 carbon aryl radicals and equivalents thereof.

Similarly, besides unsubstituted N-vinyl-Z-oxazolidinone, other N-vinyl(or 1-vinyl)-2-oxazolidinone products which may be used as polymericadjuvants include those derived from monomers represented by theformula:

R1 t? Rg-C o=o TRIP-CH2 in which at least one of the substituent R R Ror R groups, when it is not hydrogen, may be a 1 to about 4 carbon atomalkyl radical or a 6 to about 10 carbon atom aryl radicals or theirequivalents. Typical of such monomers may be mentionedN-vinyl-5-methyl-2-oxazolidinone;N-vinyl-5-chloromethyl-2-oxazolidinone; N-vinyl- 4,5 dirnethyl 2oxazolidinone, N vinyl 5 ethyl 2 oxazolidinone;N-vinyl-5-phenyl-2-oxazolidinone; and the like.

The N vinyl N methyl alkylsulfonamide monomers whose polymeric productsmay be advantageously utilized for the nitrile alloys include thoserepresented by the formula:

wherein R is hydrogen, a 1 to about 4 carbon alkyl radical, a 6 to about10 carbon aryl radical or some equivalent thereof.

Suitable nitrile alloy products may also be manufactured from otherbeneficial additaments or components that are more or less equivalent tothose derived from the azotic monomers indicated in the foregoing. Thus,other varieties of N-heterocyclic monomers more or less similar orrelated to the specified N-2-propenyl types and analogous related azoticcompounds may frequently be employed in combination with or to replacethe several beneficial additaments or constituents that have beendelineated.

What is claimed is:

1. An improvement in the textile art consisting of a destaticizingtreatment which comprises applying between about 0.5 and 10 weightpercent to a shaped nitrile alloy article an antistatic agent which is ahydrophilic derivative of a polyphcnolic polymer that is selected fromthe group consisting of those represented by the general formul e:

no 0R Ucit CH2 wherein n is a whole integer having an average value offrom about 2 to 8 and each R is independently selected from the groupconsisting of hydrogen and polyoxyethylene groups containing from 2 to20 moles of ethylene oxide with the limitation that at least onequarterand not less than 3 of the R substituents in each molecule are hydrogen;

on on R'z fion CR on ca wherein n is a number having an average value offrom about 2 to 8; each R is independently selected from the groupconsisting of hydrogen and methyl with the limitation that not more thana single R is hydrogen in any given linkage; R is selected from thegroup consisting of oxyethylene and oxypropylene; and x is a numberhaving an average value from 2 to 10;

y 07GB 2 i 2 U wherein n is a number having an average value of fromabout 3 to 8; each R is independently selected from the group consistingof oxyethylene and oxypropylene; x is a number having an average valueof from 2 to 10; each R is independently selected from the groupconsisting of hydrogen and methyl with the limitation that not more thana single R is hydrogen in any given linkage; and y is a number having anaverage value of from 1 to 10;

H oa' 6 B 'R o on wherein each A is independently selected from thegroup consisting of methylene, ethylene and propylene; each B isindependently selected from the group consisting of isopr-opylidene,sulfone and sulfinyl; R and R are independently selected from the groupconsisting of hydrogen, oxyethylene units and polyoxyethylene units ofup to moles of ethylene oxide per unit; it is a number that has anaverage value of from 2 to 8 when R is hydrogen and an average value offrom 3 to 8 when R and R are identical with the limitations that atleast three hydroxyl groups are adjacent to one another in each moleculeand at least one R per molecule is a polyoxyethylene units containing anaverage of from about 2 to 10 moles of ethylene oxide;

we on GR" accu c-cnz c-cn I I a R R wherein R and R are independentlyselected from the group consisting of hydrogen and oxyethylene; R isselected from the group consisting of hydrogen and methyl; and n is anumber having an average value of from about 2 to 8 with the limitationthat at least 3 hydroxyl substituents are present in each molecule;

wherein x is a plural number having an average value up to about 20;

wherein n is a number having an average value of from wherein n is anumber that has an average value from about 2 to 8; and each R isselected from the group consisting of para-hydroxyphenyl andpolyoxyethylated oxyphenyl units containing up to 20 moles of ethyleneoxide with the limitations that at least one R is a polyoxyethyleneoxyphenyl unit and not less than two of them are para-hydroxyphenyls;and mixtures thereof, said nitrile alloy being selected from the classof synthetic polymer compositions consisting of (A) intimate polymerblends comprised essentially of (Al) at least about 8'0 weight percent,based on composition weight, of an acrylonitrile addition polymer with(A2) up to about 20 weight percent, based on composition weight, of anazotic polymeric dye-assisting adjuvant selected from the groupconsisting of addition polymers of at least about 50 weight percent,based on the weight of the azotic polymer of (A2a) N-vinyl lactammonomers; (A212) N- viny1-3-morpholinone monomers of the structure:

0 RCH HCR RdH =0 wherein each substituent R unit is independentlyselected from the group consisting of hydrogen, 1 to about 4 carbon atomalkyl substituents and -6 to about 10 carbon atom aryl substituents;(A2c) N-vinyl-Z-ox-azolidione monomers of the structure:

HC=OH in which R R R and R are independently selected from the groupconsisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and6 to about 10 carbon atom aryl substituents; (A2d)N-vinyl-N-methyl-alkylsulfonamide monomers of the structure:

position weight, of a pre-formed acrylonitrile addition polymersubstrate with graft copolymerized substituents thereon of (B2) up toabout weight percent, based on composition weight, of additionpolymerized azotic monomer substituents of at least about Weightpercent, based on the weight of graft copolymerized substituent, or(B2a) N-vinyl lactam monomers; (B212) said N-vinyl- 3 morpholinonemonomers; (B20) said N -vinyl-2- oxazolidinone monomers (B2d) saidN-vinyl-N-methylalkylsulfonamide monomers; and (B2e) mixtures thereof;and (C) graft copolymers comprised essentially of (C1) at least about 80weight percent, based on composition Weight, of acrylonitrile graftcopolymerized on (C2) up to about 20 weight percent, based oncomposition Weight, of a pre-formed, dye-assisting, azotic additionpolymer substrate of at least about SOweight percent, based on theweight of said substrate, of (C2a) N-vinyl lactam monomers polymerizedin the substrate; (C2b) said N-vinyl-3-morpholinone monomers polymerizedin the substrate; (C20) said N-vinyl-2-oxazolidinone monomerspolymerized in the substrate; (C2d) said N-vinyl-N-methyl-alkylsulfon-amide monomers polymerized in the substrate; and(C22) mixtures thereof.

2. The treatment of claim 1, wherein said nitrile alloy is comprised ofan intimate composition of polyacrylonitrile and polymerizedN-vinyl-2-pyrrolidone.

3. The treatment of claim 1, wherein the antistatic agent is apolyphenolic compound of the structure:

cHg l" OH J2 (VII) 4. The treatment of claim 1, wherein between about1.0 and 2.0 percent by weight of said antistatic derivative of thepolyphenolic polymer is applied to said nitrile alloy substrate.

5. The treatment of claim 1, wherein the antistatic derivative of thepolyphenolic polymer is applied from a liquid dispersion and includingthe step of drying the shaped nitrile alloy after application of saidderivative.

6. The treatment of claim 1, wherein the shaped 11itrile alloy articlesubstrate is in an aquagel condition and including the steps of applyingthe derivative of a polyphenolic polymer from a liquid dispersion byimmersing the shaped nitrile alloy aquagel article therein CHQ t 6 andsubsequently drying the shaped article after application of saidderivative.

7. A treatment in accordance with the treatment set forth in claim 6,wherein said shaped article is an article in filamentary form.

8. The treatment of claim 1, wherein said antistatic derivative of thepolyphenolic polymer is applied to said shaped nitrile alloy articlewhile the latter is in an undyed condition.

9. The treatment of claim 1 and including the additional step of dyeingsaid shaped nitrile alloy article prior to said application of saidantistatic derivative of the polyphenolic polymer.

10. A shaped article comprising a substrate of a synthetic nitrile alloypolymeric material characterized in being substantially free when dryfrom propensity to accumulate static electrical charges, said articlehaving between about O.5 and 10 Weight percent of a derivative of apolyphenolic polymer applied thereto as an antistatic agent, saidantistatic derivative of a polyphenolic polymer being selected from thegroup of those having the generic Formulae I, Ila, 1119, III, IV, Va,Vb, VI and mixtures thereof, said nitrile alloy being selected from theclass of synthetic polymer compositions consisting of (A) intimatepolymer blends comprised essentially of (A1) at least about weightpercent, based on composition weight, of an acrylonitrile additionpolymer with (A2) up to about 20 weight percent, based on compositionweight, of an azotic polymeric dye-assisting adjuvant selected from thegroup consisting of addition polymers of at least about 50 weightpercent, based on the Weight of the azotic polymer, of (A2a) N-Vinylla-ctam monomers; (A2b) N-vinyl-3-morpholinone monomers of thestructure:

in which R R R and R are independently selected from the groupconsisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and6 to about 10 carbon atom aryl substituents; (A211!)N-vinyl-N-methyl-alkysulfonamide monomers of the structure:

wherein R is selected from the group consisting of hydrogen, 1 to about4 carbon atom alkyl substituents and 6 to about 10 carbon atom arylsubstituents; and (A2e) mixtures thereof; (B) graft copolymers comprisedessentially of (B1) at least about 80 weight percent, based oncomposition weight, of a pre-formed acrylonitrile addition polymersubstrate with graft copolymerized substituents thereon of (B2) up toabout 20 weight percent, based on composition weight, of additionpolymerized azotic monomer substituents of at least about 50 Weightpercent, based on the weight of graft copolymerized substituent, of(B2a) Nviny1lactam monomers; (B212) said N-vinyl-3-morpholinonemonomers; (B20) said N-vinyl- 2-oxazolidinone monomers (B2d) saidN-vinyl-N-methyl alkylsulfonarnide monomers; and (B20) mixtures thereof;and (C) graft copolymers comprised essentially of (Cl) at least about 80weight percent, based on composition weight, of acrylonitrile graftcopolymerized on (C2) up to about 20 weight percent, based oncomposition weight, of a pro-formed, dye-assisting, azotic additionpolymer substrate of at least about 50 weight percent, based on theweight of said substrate, of (C2a) N-vinyl lactam monomers polymerizedin the substrate; (C2b) said N-vinyl-3-morpholinone monomers polymerizedin the substrate; (C20) said N-vinyl-Z-oxazolidinone monomerspolymerized in the substrate; (C2d) said N-vinyl-N-methyl-alkylsulfonamide monomers polymerized in the substrate;and (C22) mixtures thereof.

11. A shaped article comprising a substrate of a synthetic nitrile alloypolymeric material, said nitrile a1- loy being selected from the classof synthetic polymer compositions consisting of (A) intimate polymerblends comprised essentially of (A1) at least about 80 weight percent,based on composition weight, of an acrylonitrile addition polymer with(A2) up to about 20 weight percent, based on composition weight, of anazotic polymeric dye-assisting adjuvant selected from the groupconsisting of addition polymers of at least about 50 weight percent,based on the weight of the azotic polymer, of (A2a) N- vinyl lactammonomers; (A2b) N-vinyl-3-morpholinone monomers of the structure:

wherein each substituent R unit is independently selected from the groupconsisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and6 to about 10 carbon atom aryl substituents; (A20)N-viny1-2-oxazo1idinone monomers of the structure:

in which R R R and R are independently selected from the groupconsisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and6 to about 10 carbon atom aryl substituents; (A2d)N-vinyl-N-methyl-alkysulfonamide monomers of the structure:

wherein R is selected from the group consisting of hydrogen, 1 to about4 carbon atom alkyl substituents and 6 to about 10 carbon atom arylsubstituents; and (A28) mixtures thereof; (B) graft copolymers comprisedessen tially of (B1) at least about weight percent, based on compositionweight, of a pre-formed acrylonitrile addition polymer substrate withgraft copolymerized substituents thereon of (B2) up to about 20 weightpercent, based on composition weight, of addition polymerized azoticmonomer substituents of at least about 50 weight percent, based on theweight of graft copolymerized substituent, of (B211) N-vinyl lactammonomers; (B2b) said N-vinyl-3-morpholinone monomers; (B20) saidN-vinyl- 2-oxazo lidinone monomers (B2d) saidN-vinyl-N-methylalkylsulfonamide monomers; and (B2e) mixtures thereof;and (C) graft copolymers comprised essentially of (C1) at least about 80weight percent, based on composition weight, of acrylonitrile graftcopolymerized on (C2) up to about 20 weight percent, based oncomposition weight, of a pre-formed, dye-assisting, azotic additionpolymer substrate of at least about 50 weight percent, based on theweight of said substrate, of (C212) N-vinyl lactam monomers polymerizedin the substrate; (C2b) said Nvinyl-3-morpholinone monomers polymerizedin the substrate; (C20) said N-vinyl-2-oxazolidinone monomerspolymerized in the substrate; (C2d) said N-vinyl-N-methyl-alkylsulfonamide monomers polymerized in the substrate;and (C2e) mixtures thereof; said shaped nitrile alloy article substratecharacterized in being substantially free when dry from propensity toaccumulate static electrical charges, said article having between about0.5 and 10 weight percent of a derivative of a polyphenolie polymerapplied thereto as an antistatic agent, said antistatic derivative of apolyphenolic polymer being selected from the group consisting of thosehaving the generic Formulae: I, Ila, IIb, III, IV, Va, Vb, VI andmixtures thereof.

12. The article of claim 11, wherein the derivative of the polyphenolicpolymer has the structure of Formula VII.

13. The article of claim 11, wherein between about 1:0 and 2.0 percentby weight of the antistatic derivative of the polyphenolic polymer isapplied thereto, based on the dry weight of the shaped nitrile alloyarticle.

14. A nitrile alloy fiber article in accordance with the article ofclaim 11, wherein said nitrile alloy is comprised of an intimatecomposition of polyacrylonitrile and polymerized N-vinyl-2-pyrrolidone.

15. An article in accordance with the article set forth in claim 14,characterized in being undyed and resistant to staining by dyestuffs andcoloring agents.

16. An article in accordance with the article set forth in claim 14,characterized in consisting of a dyed acrylonitrile polymer substrateover which said antistatic derivative of the polyphenolic polymer isapplied.

References Cited in the file of this patent UNITED STATES PATENTS2,454,541 Beck et al Nov. 23, 1948 2,519,013 Banigan Aug. 15, 19502,558,734 Cresswell July 3, 1951 2,676,896 Cohen et al. Apr. 27, 1954

1. AN IMPROVEMENT IN THE TEXTILE ART CONSISTING OF A DESTATICZINGTREATMENT WHICH COMPRISES APPLYING BETWEEN ABOUT 0.5 AND 10 WEIGHTPERCENT TO A SHAPED "NITRILE ALLOY" ARTICLE AN ANTISTATIC AGENT WHICH ISA HYDROPHILIC DERIVATIVE OF A POLYPHENOLIC POLYMER THAT IS SELECTED FROMTHE GROUP CONSISTING OF THOSE REPRESENTED BY THE GENERAL FORMULA: